Fabric softening compositions containing quaternary allophanoylmethylammonium compounds

ABSTRACT

Quaternary allophanoylmethylammonium compounds having the formula   wherein R1 and R2 individually represent aliphatic hydrocarbons having 10 to 24 carbon atoms, R3 represents alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms or cyanoalkyl having 1 to 4 carbon atoms, R4 and R5 individually represent hydrogen or alkyl having 1 to 3 carbon atoms and X represents an anion of an inorganic or organic acid; as well as the method of preparation of these quaternary allophanoylmethylammonium compounds, compositions containing the same and the method of softening washed textiles utilizing said compounds in the rinse liquor.

United States Patent 11 1 Eekert et a1.

1451 Nov. 11, 1975 1 FABRIC SOFIENING COMPOSITIONS CONTAINING QUATERNARY ALLOPHANOYLMETHYLAMMONIUM COMPOUNDS [751 Inventors; Hans-Werner Eekert, Dusseldorf; Peter Nikolaus, Dusseldorf-Holthausen; Johann Sehwarzer Monheim. all of German [73] Assignee: Henkel 84 Cie G.m.b.H.. Dusseldorf.

Germany 122] Filed; May 21, 1973 {21] App]. No: 362,314

[3(1) Foreign Application Priority Data May 19 1972 Gcrman 2224553 [521 U.S. C1 252/83: 260/553 13:428/272: 428/274 [51] Int. Cl. DOfiM 13/46; C(J7C 127/22 {58] Field of Search 4 252/854; 117/1395 CO; 260/553 E [5m References Cited UNITED STATES PATENTS 2.253.773 8/1941 Engel et 252/814 X 31165.1 10 11/1962 Hagge et a1 117/1395 X 3.256.181) (1/1966 Weiss et 252/88 3.6442(14 211972 Heins ct dimmer. v L l/81R FORElCiN PATENTS OR APPLICATlONS 2014.131 M1940 Snitlcrlantl 2(\(Il'553 E Primary litumim'r Herbert B. Guynn Attorney. Agent. or Hrm Hammond t5: Littell [S 7 ABSTRACT Quaternar allophano;lmetlnlammoniuin compounds having the formula wherein R and R individuall represent aliphatic hydrocarbons having It) to 24 carbon atoms. R represents a1k \l having 1 to 4 carbon atoms. l1}Ll1'OXL1l1-( \'l having 1 to 4 carbon atoms or eyanoalk \l having 1 to 4 carbon atoms. R and R indiriduallx represent hy drogen or alkyl having 1 to 3 carbon atoms and X" represents an anion 01 an inorganic or organic acid; as well as the method of preparation of these quaternar a1lophanoylmethylammonium compounds composi tions containing the same and the method of softening washed textiles utilizing said compounds in the rinse liquor.

9 (l-aims, N0 Drawings FABRIC SOFTENING COMPOSITIONS CONTAINING QUATERNARY ALLOPI-IANOYLMETI-IYLAMMONIUM COMPOUNDS THE PRIOR ART After the drying of washed textiles, particularly those of cotton or similar cellulose fibers, a distinct hardening or harshening of the handle or hand can be observed. This phenomenon is particularly exhibited if the textiles have been washed in drum-washing machines with a strong mechanical agitation. This undesirable hardening of the textile goods can be avoided. as is well-known, when a softening rinsing agent is added to the last rinsing liquor of the washing process, that conventionally contains cationic compounds with at least two longer-chain alkyl radicals in the molecule. There are liquid softening rinsing agents for laundry on the market which contain as active ingredient distearyldimethylammonium chloride, in an aqueous dispersion. It is known, however, that such cationic softening rinsing agents adversely effect the absorptivity of the treated laundry, even when the instructions for use'are followed exactly.

OBJECTS OF THE INVENTION An object of the present invention is the obtention of softening agent compounds and compositions which effectively soften washed textiles without an adverse effect on the absorptivity of the treated laundry.

Another object of the present invention is the development of a quaternary allophanoylmethylammonium compound having the formula wherein R and R are individually members selected from the group consisting of alkyl having l to 24 carbon atoms, alkenyl having l0 to 24 carbon atoms and alkadienyl having to 24 carbon atoms, R is a member selected from the group consisting of alkyl having 1 to 4 carbon atoms, hydroxyalkyl having I to 4 carbon atoms and cyanoalkyl having from 1 to 4 carbon atoms, R and R are individually members selected from the group consisting of hydrogen and alkyl having 1 to 3 carbon atoms, and X represents the anion of an acid selected from the group consisting of inorganic acids and organic acids having I to 4 carbon atoms.

A further object of the present invention is the development of a process for the production of the above quaternary allophanoylmethylammonium compounds consisting of the steps of reacting substantially equimolar amounts of an a-haloacylurea having the formula wherein R, and R are individually members selected from the group consisting of hydrogen and alkyl having 1 to 3 carbon atoms, and Hal represents a halogen, with a tertiary amine having the formula wherein R and R are individually members selected from the group consisting of alkyl having 10 to 24 carbon atoms. alkenyl having it) to 24 carbon atoms and alkadienyl having [0 to 24 carbon atoms, R is a member selected from the group consisting of alkyl having I to 4 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms and cyanoalkyl having from 1 to 4 carbon atoms, at a temperature of from 50C to [00C, and recovering said quaternary allophanoylmethylammonium compounds.

A yet further object of the present invention is the obtention of a liquid or powdery softening agent composition for washed textiles consisting essentially of a. from 1 to 50% by weight of a quaternary allophanoylmethylammonium compound having the formula wherein R and R are individually members selected from the group consisting of alkyl having l0 to 24 carbon atoms, alkenyl having 10 to 24 carbon atoms and alkadienyl having 10 to 24 carbon atoms, R, is a member selected from the group consisting of alkyl having I to 4 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms and cyanoalkyl having from I to 4 carbon atoms, R, and R are individually members selected from the group consisting of hydrogen and alkyl having 1 to 3 carbon atoms, and X represents the anion of an acid selected from the group consisting of inorganic acids and organic acids having 1 to 4 carbon atoms.

b. from 0 to l0% by weight of at least one nonionic surface-active dispersing agent selected from the group consisting of a water-soluble dispersing agent and a waterdispersible dispersing agent.

c. from 0 to 25% by weight of other customary ingre clients of softening agents for washed laundry, and

d. the remainder up to by weight of at least one diluent selected from the group consisting of water, and water-soluble or readily water-dispersible liquid and solid carriers.

A further object of the invention is the development of a process for the softening of washed textiles which consists of rinsing said washed textiles with water containing from 0.05 to 1.0 gm/] of the above quaternary allophanoylmethylammonium compound.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE lNVENTlON It has now been found that novel aliphatic N,N,N-trisubstituted N-allophanoylmethylammonium compounds of Formula I:

in which R and R individually represent aliphatic hydrocarbon residues having it) to 24. preferably 12 to 18 carbon atoms.

R represents an optionally substituted alkyl residue with l to 4 carbon atoms. R. and R individually represent hydrogen or an alkyl residue with l to 3 carbon atoms. and X represents an anion of acid. especially the chloride anion. suprisingly have outstanding washinglmprovement properties and are suitable for use as textile softeners. especially in washing after-treatment agents. in addition to the good softening action. the property which the new compounds have of only affecting the absorptive capacity of the treated fabric to an inconsiderable extent is particularly advantageous. Moreover. by the treatment with the compounds according to the invention an undesired static charging of the textiles. especially those made of synthetic fibers, is largely prevented. The treated textiles are further found to require little ironing.

More particularly. the invention relates to a quaternary allophanoylmethylammonium compound having the formula wherein R and R are individually members selected from the group consisting of alkyl having it) to 24 car bon atoms. alkenyl having it) to 24 carbon atoms and alkadienyl having it] to 24 carbon atoms. R is a member selected from the group consisting of alkyl having I to 4 carbon atoms. hydroxyalkyl having 1 to 4 carbon atoms and cyanoalkyl having from 1 to 4 carbon atoms. R and R are individually members selected from the group consisting of hydrogen and alkyl having 1 to 3 carbon atoms, and X represents the anion of an acid selected from the group consisting of inorganic acids and organic acids having 1 to 4 carbon atoms.

Antimicrobial substances and optical brighteners can be readily incorporated with the new textile softeners in liquid and solid compositions.

The aliphatic hydrocarbon residues R. and R in the Formula l may be straight or branched chain. saturated or unsaturated residues of synthetic or natural origin. Specially preferred residues R and R are the straightchain alkyls. for example. decyl. dodecyl. tetradecyl.

hexadecyl. octadecyl. eicosyl. docosyl and tetracosyl.

In addtion. the residues R and R may be derived from naturally occurring fatty acids. For the substituent R alkyls having l to 4 carbon atoms. such as methyl. ethyl. propyl or butyl are suitable. as well as substituted alkyl residues such as hydroxyalkyl and cyanoalkyl. for example. Z-hydroxyethyl or 2-cyanoethyl. Methyl is of particular practical interest. The residues R. and R may be the same or different. They preferably represent hydrogen or methyl or ethyl.

The anion X limited by the process of preparation further described below. is especially a halide anion. preferably the chloride anion. The quaternary ammonium compounds of Formula I according to the inven- 4 tion. however. can be converted in known way into salts with other anions of inorganic acids and organic acids. such as sulfates. borates. phosphates, perchlorates. and salts of organic acids. if this is desired. for example. to obtain a better processability.

ln admixture with the other constituents of the various forms of application. especially liquid forms. at least a part of the original anions X could and probably would be replaced by other acid residues. which are generally introduced into the preparations of the invention as alkali metal salts and in this form represent the usual components of washing after-treatment agents.

The new substances of Fonnula l are solid at normal temperature. readily soluble or dispersible in water. they are also very soluble in the lower alcohols such as methanol. ethanol and isopropyl alcohol.

The invention further relates to a process for the preparation of the new substances of Formula I. In this process about 1 mol of an a-haloacylurea of Formula lla Hal CR..R,-.CONHCONH (llu) is reacted with 1 mol of a tertiary amine of Formula llb NR|R2R3 (lib) in which Formulae. the residues R to R,-. have the above-defined meanings for Formula I. and Hal represents a halogen. for example. chlorine or bromine. at a temperature of from 50C to l0OC. preferably in an organic solvent.

The product is obtained after removing the solvent e.g. by distillation. and is generally used in this form for technical purposes. In some cases. a purification by re dissolving or recrystallization can be utilized. for example. from acetone. ethyl acetate. acetonitrile. isopropyl alcohol, or mixtures of these solvents with one another. optionally with use of active charcoal or other adsorbents.

The condensation products of an a-halocarboxylic acid halide with urea. for example. chloroacetylurea. a-chloropropionylurea. oz-bromobutyrylurea. a chloroisobutyrylurea and so on. are used as the ahaloacylurea of Formula llu. Chloroacetylurea is preferred where R. and R are hydrogen.

The tertiary aliphatic amines of Formula llb used in the process according to the invention are. for examle. didodecylmethylamine. ditetradecylmethylamine. Elihexadecylmethylamine. dioctadecylmethylamine. didodecyl-( Z-hydroxyethyl l-amine. ditetradecylisopropylamine. didodecylisobuty'lamine. etc. Tertiary aliphatic amines of Formula llb in which R, and R represent residues derived from fatty acids of natural origin are also of practical interest. for example. coconut fatty acid. tallow fatty acid. soya fatty acid. rape oil fatty acid. or their hydrogenation products. Such tertiary amines are. for example. ditallow-alkylmethylamine. di-coconut-alkylrnethylamine, etc.

organic solvents which may be used in the process of preparations are. for example. the lower alcohols such as methanol. ethanol. isopropyl alcohol. butanol. and also acetonitrile. glycol. ethyleneglycol-monomethyl and -dimethyl ethers. dimethylformamide and dimethylsulfoxide. and possibly mixtures of these solvents with water.

The compounds listed in Table 1 below are some of the quaternary allophanoylmethyl ammonium compounds of Formula I according to the invention.

TABLE I l. NN-Didodecyl-N-methyl-N-allophanoylmethylammonium chloride:

NN-Ditetradeey l-N-methyl-N-allophanoy lmethy lammonium chloride;

TABLE l-continued 3. N ,N,-Dihexaldec l-N-methy l-N-allophanoylmethylammonium chloride;

4, N.N-Dioctadecyl-N-meth)LN-allophanoylmethylammonium chloride;

5, NN-Ditallon-alkyl-N-methyl-N-allophanoylmethylammonium chloride;

6. N.N-Dicoconut-alkyl-N-methyl-Nallophanoylmethylammonium chloride: 7, NN-Didodecyl-NJI-hydrox eth l)-N-allophanoylmethylammonium chloride; 8. NA-Ditetradecyl'Nisopropyl-N-1illophz|noylmethylammonium chloride; 9. N.N-Didodecyl-X-isohutyLNallophanoylmethylammonium chloride; N,N-Dieicosyl Nmethyl-N-allophanoylmethylammnnium chloride: N,N-Didocosyl-N-methyl-Nallophanoylmethylammonium chloride: 12. N .N-Ditetracosyl-N-methyl-N -allophanoylmethy [ammonium chloride; N.N-Dltetradec l-Nmeth l-N-l l-allophanoyl-ethyllammonium chloride; N.N-Ditetradec l-N-methyl-l i-l l-u|lophuno l-prop}llammonium bromide. NN-Ditetradec l-N-methylN-l l-a|lophanoyl-isopropyl ammonium chloride,

The further treatment of the laundry with the compounds of Formula 1 may be effected in various ways depending on the drying process, which is to be used. if the drying is carried out in a hot air drier, the washed laundry can be directly sprayed with a dispersion of the active substance or the latter may be brought into contact with the washed laundry by way of a carrier, for example by spraying the inside walls of the drier with the dispersion of active substance before the drier is charged with the wash or by the addition to the charge of a carrier of large surface area saturated with the dispersion of active substance, whereby the textile softener is absorbed on the washed goods during the drying process. At the present time, however, the washing is generally hung out to dry, therefore the application of the softener in the last rinsing bath in a washing process when done by hand, and especially by machine washing, is most commonly used. Of course, this procedure can be followed where the wash is dried in a drier also. -ln the last-mentioned application, the compound of Formula 1 is preferably used in the rinsing bath in amounts from 0.05 to 1.0 gm/liter, especially from 0.1 to 0.5 gm/liter.

In addition, other substances may be present in the rinsing bath, which substances are usable for the aftertreatment of washed laundry, such as optical brighteners, anti-microbial active agents, souring agents, sequestering agents, perfumes and dyes, etc. At least part of these substances should be acidic, and the amount of the acidic substances, particularly of the souring and sequestering agents is selected so that the rinsing bath has a neutral to weakly acidic pH range.

In a further aspect the invention relates to the use of the compounds of Formula according to the invention as textile softeners in washing after-treatment compositions.

Said washing after-treatment composition is more particularly a liquid or powdery softening agent composition for washed textiles consisting essentially of a. from 1 to 50% by weight of a quatemary allophanoylmethylammonium compound having the formula wherein R and R are individually memebers selected from the group consisting of alkyl having 10 to 24 carbon atoms. alkenyl having 10 to 24 carbon atoms and alkadienyl having 10 to 24 carbon atoms. R; is a member selected from the group consisting of alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms and cyanoalkyl having from 1 to 4 carbon atoms, R, and R are individually members selected from the group consisting of hydrogen and alkyl having I to 3 carbon atoms, and X represents the anion of an acid Selected from the group consisting of inorganic acids and organic acids having 1 to 4 carbon atoms.

b. from 0 to 10% by weight of at least one nonionic surface-active dispersing agent selected from the group consisting of a water soluble dispersing agent and a water-dispersible dispersing agent,

0. from 0 to 2571 by weight of other customary ingredients of softening agents for washed laundry. and

d. the remainder up to by weight of at least one diluent selected from the group consisting of water. and water-soluble or readily water-dispersible liquid-and solid carriers.

According to the invention the new substances can be used as textile softeners in pulverulent or liquid washing after-treatment compositions. which contain, besides the said substances, at least one diluent for these substances and, optionally, other usual components of washing after-treatment compositions.

Suitable liquid carriers or diluents are water and water-soluble organic solvents from the group of lower alcohols containing 1 to 5 carbon atoms; preferably alkanols having 1 to 5 carbon atoms, for example, methanol, ethanol, propanol, isopropyl alcohol, butanol, amyl alcohol, lower ketones, preferably alkanones having 3 to 6 carbon atoms, such as acetone and methylethylketone and the ethyleneand diethylene glycols and their monomethyl or dimethyl, or monoethyl or diethyl ethe rs, as well as mixtures of the same with water.

Water and isopropyl alcohol-water mixtures are of special practical interest.

Solid carriers or diluents which may be used are readily watersoluble or water-dispersible inert inorganic or organic compounds especially from the group comprising urea. acetamide, biuret, sodium sulfate. solid polyethylene glycols and, optionally, solid forms of the below listed acid additives and acid sequestering agents.

The other components of the after-treatn agents according to the invention consist essentially of dispersing agents, especially non-ionic dispersing agents, optical brighteners, antimicrobial active agents, acid additives or souring agents, solution aids, perfumes and dyestuffs.

For the preparation of solid pulverulent washing after-treatment agents, the quaternary allophanoylmethylammonium compounds, according to the invention, dissolved in organic solvents, may be sprayed on the moving solid carrier substances. For this purpose. carrier substances with the largest possible surface and a low bulk weight, for example a bulk weight of 100 to 700 gm/l are preferably used. Products of such bulk weight are obtained, for example, by calcining inor ganic salts containing water of crystallization. When urea is used as the carrier substance. the active substances can also be mixed with the molten urea. to which. means for lowering the melting point has been added. and the melt converted into a powder. In all cases the powder properties can be improved by incorporation of small quantities of substances with a large surface a eu as. for example. microcrystalline silicic acid. magnesium silicate. and so on.

The composition of the powdery washing after-treat ment agents for laundry of the invention lies generally in the range of the following formulation based on the anhydrous substances:

1 to 50%. preferably 2 to 20% and more particularly 5 to by weight of the above quaternary allophanoylmcthylammonium compounds,

0 to 10%. preferably 0.2 to 6% and more particularly 0.5 to 3% by weight of a dispersing agent. preferably a nonionic dispersing agent.

0 to preferably 0.3 to l5% by weight of other customary ingredients of washing after-treatment agents for laundry.

Remainder. solid carriers from the group of urea. acetamidc. biuret. sodium sulfate. solid polyethylene glycols.

Of the other customary ingredients of solid washing after-treatment agents for laundry at least one of the following components may be present. in the stated amount. based on the whole composition;

from 0.2 to 5.0% by weight of antimicrobial active substance.

from 01 to 10.0% by weight of an acid additive,

from 0.0] to 0.8% by weight of cotton brighteners.

from 0.01 to 0.8% by weight of polyamide brighteners.

from 0.01 to 0.8% by weight of perfume.

from 0.0000l to 0.08% by weight of dye.

The powdery agents of the invention are utilized in such amounts that the concentration of the textile softener is in the range offrom 0.05 to 1.0 gm/l of the aqueous treatment liquor.

In practice. the composition of particularly interesting liquid washing after-treatment compositions, in which the above-defined new substances according to the invention are utilizable. generally lies within the range of the following formulation:

2.0 to 20%. preferably 5 to 15% by weight of a substance of Formula I,

0.2 to 6%. preferably 0.5 to 3% by weight of dispersing agents. preferably non-ionic dispersing agents.

0 to preferably 1 to l5% by weight of water-soluble organic solvents.

0 to l0%. preferably 0.3 to 7.5% by weight of other usual components of washing after-treatment agents.

Remainder water.

At least one of the following components may be present in the given amounts. referred to the total composition. as the other usual components of washing aftertreatment agents.

0.2 to 3.0 by weight of an antimicrobial active substance.

0.2 to 6.0 by weight of acid additives.

0.01 to 0.5 by weight of a cotton brightener.

0.01 to 0.5 by weight of a polyamide brightener.

0.01 to 0.5 by weight of perfume.

0.00001 to 0.05% by weight of dyestuff.

These liquid agents are prepared by mixing the com ponents.

The liquid and solid agents according to the invention are distinguished by a good dispersibility in cold water. With the treatment of washed laundry by the softening agents for laundry of the invention. fabrics hardened by washing. particularly cotton terry cloth. become soft and nappy. Such treated fabrics possess. in comparison to the untreated washing goods. only a slightly diminished absorptivity and in comparison to the washing goods treated with known cationic softeners. a substantially improved absorptivity. In addition. by the treatment with the agents. according to the invention. an undesirable static charging of the textiles particularly those of synthetic fibers. is largely prevented.

The components contained in the washing aftertreatment agents of the invention are described below. in addition to the quaternary allophanoylmethylammonium compounds and the carrier substance. and are described more particularly by their various classes.

Suitable dispersing agents. which may be contained in the liquid and pulverulent washing after-treatment compositions are especially the non-ionic surface-active substances. referred to below as nonionics. These include products which owe their hydrophilic properties to the presence of polyether chains. ami neoxide. sulfoxide or phosphine oxide groups. alkylolamide groups as well quite generally to an excess of hydroxyl groups. Such nonionics contain in the molecule at least one hydrophobic radical of 8 to 26. preferably l0 to 20 and particularly [2 to l8 carbon atoms. and at least one nonionic watcr-solubilizing group. The preferably saturated hydrophobic radical is mostly of an ali phatic. optionally also alicyclic nature. It can be connected directly to the hydrophilic groups or over connecting members. As connecting member. for instance. benzene rings. carboxylic acid ester or carbonamide groups. ether-like or ester-like bound radicals of polyhydric alcohols. such as those of the ethylene glycol. the propylene glycol. the glycerine or of corresponding polyether radicals. are of interest.

Of particular practical interest are the products ob tained by addition of ethylene oxide and/or glycide to fatty alcohols. alkylphenols. fatty acids. fatty amines. fatty acid or sulfonic acid amides having the above hydrophobic radicals. These nonionics may contain from 4 to 100. preferably 6 to 40 and particularly 8 to 20 ether groups. above all ethylene glycolether groups. per molecule. in addition. in these polyether chains or at their end. propylene or butyleneglycolether groups or polyether chains may be present.

Further suitable non-ionic surface-active compounds are the water-soluble products of the addition of ethylene oxide to polypropylene glycol Pluronics or to al kylenediaminepolypropylene glycol Tetronics. They are obtained from polypropyleneglycols. themselves water-insoluble. or from water-insoluble propoxylated lower aliphatic alcohols containing 1 to 8. preferably 3 to 6 carbon atoms. or from water-insoluble propoxylated alkylenediamines. These water-insoluble (i.e. hydrophobic) propylene oxide derivatives are con- .verted into the said non ionics by ethoxylation until the products are water-soluble. Finally. the reaction products of the above-mentioned aliphatic alcohols with propylene oxide known as UcomFluidsome of which are still water-soluble. are utilizable as nonionics.

In addition. the fatty acid or sulfonic acid alkylolamides which are derived. for instance. from mono or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines. for instance the glycamines tives of the diaminostilbene-disulfonic acid are compounds according to formula lll:

are in the class of useable nonionics. They can be replaced by amides of higher primary or secondary alkylamines and polyhydroxy carboxylic acids.

Nonionic surface-active compounds of the amineoxide type are also utilizable. The nonionic surface-active amincoxides include, for example, the products derived from higher tertiary amines having a hydrophobic alkyl residue and two shorter alkyland/or alkylol residues containing up to 4 carbon atoms each.

As nonionic dispersing agents. optionally suitable are also water-soluble or water-emulsifiable or dispersible compounds, which contain no hydrophobic radicals in the sense of the above-described nonionic surface-active agents or in which the nature or the number ofhydrophilic groups is insufficient to attain a complete watensolubility. The former includes compounds such as solid or liquid polyethylene glycols, ethylene oxide adducts of glycerine and other polyalcohols, etc. The latter include, for example. partial fatty acid glycerides or water-insoluble or not completely water-soluble alkoxylation products, for example those with 2 to 5 ethylene glycolether residues in the molecule.

Useful water-soluble organic solvents are the lower alcohols having 1 to 5 carbon atoms, as for example, methanol, ethanol, propanol, isopropyl alcohol, butanol, amyl alcohol, and also the lower ketones as for example, acetone and methylethylketone, as well as ethyleneglycol and diethyleneglycol and their monoor di-methyl or ethyl ethers. lsopropyl alcohol is of special practical interest.

Inorganic and non-surface-acting organic acids, in-

nocuous to the fibers to be treated with 2 to 8 carbon v atoms, optionally in the form of their slightly acidic water-soluble salts, such as their alkali metal salts, are suitable as acid additives or souring agents, such as amidosulfonic acid, urea compounds of orthophosphoric acid, boric acid, oxalic acid, lactic acid, glycolic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, gluconic acid. acetic acid and propionic acid as well as benzene, toluene or xylene sulfonic acids, sulfoacetic acid or sulfobenzoic acids. Preferably the acid additives are hydroxyalkanoic acids having 2 to 8 carbon atoms, hydroxyalkanedioic acids having 3 to 8 carbon atoms, dihydroxyalkanedioic acids having 4 to 8 carbon atoms, hydroxyalkanetrioic acids having 4 to 8 carbon atoms and alkanoic acids having 2 to 8 carbon atoms.

Urea and lower carboxylic acid amides, preferably lower alkanoic acid amides, for example, acetamide, and the potassium salts of benzene, toluene, or xylene sulfonic acids, sulfoacetic acid or sulfobenzoic acid may be used as solution aids.

The useable brighteners are mostly, if not exclusively. derivatives of aminostilbene-sulfonic acid or diaminostilbene-sulfonic acid, diarylpyrazolines, carbostyril, l ,2-di-( Z-benzoxazolyl )-or l ,2-di-( Z-benzimidazolyl)-ethylene, benzoxazolyl-thiophene and coumarins.

Examples for brighteners from the class of the deriva- In the formula R and R signify alkoxy groups, amino groups or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines, or residues of aminosulfonic acids, while aliphatic residues present in the above groups preferably contain l to 4 and especially 2 to 4 carbon atoms, and in the hcterocyclic ring systems. five-or sixmembered rings are usually of interest. Aniline, anthranilic acid or anilinesulfonic acid residues are preferred as the aromatic amines. Brighteners derived from diaminostilbenesulfonic acid are mostly used as cotton brighteners. The following products derived from the above formula [II in which R represents the residue -NHC.,H and R may represent the following residues, are at present on the market.

-NH. -NH-CH;,,

-NH-CH. -CH OCH -NH-CH. -CH ,-CH. i-O-CH;,, C H N-CH -CH OH, -N-(CH ,-CH OH) morpholino-. -NH-C.,l-l,-,, -NH-C.,H,-SO;.H, -OCH Some of these brighteners are to be regarded as transitional types to the polyamide brighteners as regards their affinity for the fiber, for example the brightener in which R equals NHC,,H The compound 4,4'-bis- (4-phenyl-vicinal-triazolyl-l- )-stilbenedisulfonic acid- 2,2' also belongs to the cotton brighte ners of the diaminostilbenesulfonic acid type.

Diarylpyrazolines of Formulas IV and V belong to the polyamide brighteners, of which again a few have a certain affinity for cotton fibers:

in formula IV. R;, and R represent hydrogen atoms. or alkyl or aryl residues possibly substituted by carboxyl.

1 l carbonamide or ester groups.

R and R represent hydrogen or short-chain alkyl residues.

Ar and Ar represent aryl residues such as phenyl diphenyl or naphthyl. which may carry further substituents such as hydroxy. alkoxy. hydroxyalkyl. amino. alkylamino. acylamino. earboxyl. carbo\y1ic acid ester. sulfonic acid. sulfonamide and sulfone groups or halo gen atoms.

Brighteners of this type found at present on the market are derived from the formula V. and the residue R may represent the groups C1. SO NH SO- ,CH=Chand COOCH -CH OCH while the residue R in all cases represents a chlorine atom. 9 Cyano-anthracene is also on the market as a polyamide brightener.

1n addition. aliphatic or aromatic substituted aminocoumarins belong to the polyamide brighteners, for example 4methyl-7-dimethy1aminoor 4-methyl7-diethylaminocoumarin. Further useful polyamide brighteners are the compounds l-(benzimidazo1yl-2')-2-(l\lhydroxyethyl-benzimidaZolyl-2'l-ethylene and LN- ethyl-3 phenyl-7-diethy1aminocarbostyril. Suitable brighteners for polyester and polyamide fibers are the compounds 2,5-di-( benzoxazolyl-Z )-thiophene. 2( 2 benzoxazoly 1 )-naphtho-[ 2 3-b l-thiophene and 1,2-di- (5 '-methy1-benzoxazo1y1-2' )-ethy lene.

1f the brighteners together with other components of the products of the invention are present as aqueous solutions or pastes and are converted into a solid state by hot drying. it is advisable to incorporate at least 0.1%. preferably 0.2 to 1% by weight of the solid products of organic complex-forming substances for stabilizing the brighteners.

Anti-microbial active substances are here understood as bactericidal or bacteristatic or fungicidal or fungistatic acting compounds. These active substances should be water-soluble as such. or in the form of their salts. The anti-microbial active substances. usable according to the invention. are mostly quaternary ammonium compounds. particularly those which contain, in addition to a long-chain aliphatic and two short-chain aliphatic hydrocarbon radicals, an organic radical in the molecule, either aromatic residue connected over an aliphatic carbon atom to the nitrogen atom or an aliphatic residue with double bonds. Examples for such anti-microbial quaternary ammonium compounds are the following: dimethyl-benzyl-dodecyl-ammonium chloride, dimethyl-benzyl-tetradecylammonium chlo' ride. dimethyl-( ethylbenzyl )-dodecyl-am monium chloride. dimethyl-benzy1-decyl-ammonium bromide, diethylbenzyl-dodecyl-ammonium chloride, diethylbenzyl'octylammonium chloride. dibutyl-al1yl-, methylethy1-benZy1-. ethyl-cyclohexyl-a1lyland ethyl-crotyl diethylaminoethyl-. dodecyl-ammonium chlorides.

Other usable antimicrobial active substances are the lower alcohols or diols, substituted both by bromine and nitro groups. with 3 to 5 carbon atoms, such as the compounds 2-bromo-Z-nitro-propanediol-1.3. lbromo-1nitro-3.3.3.-trichloropropanol-2. 2-bromo-2- nitro-butanol- 1.

As anti-microbial active substances. also suitable are phenolic compounds of the type of the halogenated phenols with l to 5 halo substituents. particularly chlorinated phenols; alky1-. CycloalkyL. aralkyland phenylphenols with 1 to 12 carbon atoms in the alkyl radical and with l to 4 halo substituents. particularly chlorim: and bromine in the molecule: alkylene lais phenols,

' N 7.50% O 5.71% Cl 6.33% Found:

particularly derivatives substituted by 2 to 6 halogen atoms and optionally by lower alkyl or trifluoromethyl groups with an alkylene bridge consisting of 1 to 10 carbon atoms: hydroxy benzoic acids or their esters and amides. particularly anilides which may be substituted in the benzoic acid and/or aniline radical especially by 2 or 3 halogen atoms and/or trifluoromethyl groups; 0- phenoxyphenols which may be substituted by l to 7. preferably 2 to 5 halogen atoms and/or the hydroxyl. cyano. carbomethoxy. and carboxyl group or by lower alkyl. A particularly preferred derivative of the class of o-phenoxyphenols is 2-hydroxy-2, 4.4'-trichlorodiphenyl ether.

The following specific embodiments are illustrative of the invention without being limitative in any respect.

The preparation of the new quaternary ammonium compounds is illustrated by means of the following Examples:

EXAMPLE l N.N-Didodecyl-N-methyl-N-allophanoylmethylammonium chloride 41.1 gm (0.3 mol) of chloroacetylurea. were suspended in a solution of 1 10.2 gm (0.3 mol) of didodecylmethylamine in 500 ml of isopropyl alcohol and the mixture was heated for 30 hours at about C (reflux temperature). After removing the solvent in vacuo. the reaction product was a highly viscous oil. which solidified on standing and was obtained as a solid having a melting point of 133C after recrystallizing from ethyl acetate.

The structure of the new substance was proved by the following elemental analysis and infrafred and nuclear resonance-spectroscopic data:

Elemental analysis: Cg HmrNgOgCl (504.3) Calculated: C 66.70% H 11.59% N 8.33% O 6.35% C17.03% Found: C 66.83% H 11.31% N 8.14% O 6.38% Cl 7.12%

Infrared spectrum (KBr): 3400 m, 3310 w, 3240 m, 2950 sh. 2920 s. 2850 s. 1728 m, 1706 s. 1590 m. 1468 m, 1375 m. 1210 m (s strong; in medium. w weak, sh shoulder).

Nuclear resonance spectrum (in CDCl Position in ppm against TMS (intensity): 0.90 (6); 1.25 (36); 1.8 (4): 3.6 (7); 4.95 (2); 7.1 (2) EXAMPLES 2 to 6 The following new substances of Formula 1 were obtained by the method of preparation described in Example 1. The infrared spectroscopic data agreed with those of the product of Example 1.

EXAMPLE 2 N,NDitetradecyl-N-methyl-N-allophanoylmethylammonium chloride:

M.p. 131C;

Elemental analysis: Calculated: C 68.59% H 1 1.87% C 68.62% H 12.12% N 7.64% O 571% Cl 6.34%

EXAMPLE 3 N.N-Dihexadecyl N methyI-N-a llophanoylmethylam- 1 moriium chloi'idz M.p. C;

13 14 Elemental analysis: Calculated: C 70.14% H 12.10% b. Determination of the absorption capacity (mea- N 6.82% O 5.19% Cl 5.75% Found: C 70.01% H surement of the rise in height) 12.01% N 6.99% O 5.19% Cl 5.83% The influence of the textile softening agents. used according to the invention. on the absorptivity of the cot- EXAMPLE 4 5 ton fabrics. treated with these active substances. was N.N-dioctadeeyl-N-methyl-N-al1ophanoylmethylamdetermined by the ascending method IJorder. Zeitsmonium chloride: ehrift fur die gesamte Textilindustrie. 64. 593(19621;

Mp 8pc; ibid. 67. 22 (1965)].

Elemental analysis: Calculated: c 71.43% H 12.29% A prel'iousl" l N 625% 47617! C] 527% Found: C 71.81% H nol and dlehloromethane served as test material. This 12297 N 6.03% 0 480% CI 545% test fabric was agitated with a dispersion of 0.3 gm/l and 0.5 gm/l of the test preparation for one hour. sub- EXAMPLE sequently centrifuged, dried and ironed between filter N.N-Ditallow-alkyl-N-methyl-N-allophanoylmethylam- H g?" g g i?$ i g f g monium Chloride: ml lty or ours. t cse strips. cm ong an cm wide, were suspended with their lower ends in distilled ldemfied by mfmred p pywater and the rise in height d of the water after a time 'of l. 2. 5. 10. and minutes were measured. Fab EXAMPLE 6 ric which had only been treated with water served for N,l\l-Dlcoconut-alkyl-N-methyl-N-allophanoylmecomparison. and also fabric treated with 0.3 gm/l and thylammonium chloride: 0.5 gm per liter of dioctadecyl-dimethylammoniuni chloride as a substance for comparison. l\' 8 parallel measurements were carried out. EXAMPLE 7 If the ascending height of water of the softening rinsed strip at the time j with the preparation of the invention 1' is designated as if the ascending height of the strip rinsed with water at the time j is designated as d for the absorptivity value S at the time j. that is the percentual residual absorptivity based on water (H 0) 100% is found:

Identified by infrared spectroscopy.

The usefulness of the new substances of Examples 1 to 6 as effective components of washing after-treatment compositions was determined by the following test methods.

a. Determination of the softening action u The determination of the softening action was ezfrried out with aqueous dispersions of the active substance. For this purpose, samples of cotton Terry cloth. SJ 2 X handle value 6 previously hardened in a defined way (by 240 hours treatment with 2.0 gm/liter of sodium tripolyphosphate solution under boiling washing condiand for the average absorptivity value S I tions in an automatic washing machine) were treated in the presence of clean carrier fabric with dispersions of l :311 l :30 I

the substances of Formula 1 (concentration of samples 5 z F 0.3 gm/liter and 0.5 gm/liter in the last rinsing bath of 40 F1 l a drum washing machine (Time of treatment: 5 min;

bath ratio: 1:25). The samples were then centrifuged For comparison. the ascending height 11 of test strips and hung up to dry. The estimation of the handle was was determined which were rinsed with a solution of carried out independently by 4 experienced persons the N.N-dioctadecyl-N.N-dimethyl-ammonium chloand expressed in values between 1 (full and very soft ride and from it the percentual improvement A, of the handle) and 6 (very hard handle), the handle value 1 absorptivity of the active substance i compared to N.N- referring to new cotton Terry cloth, the dressing of dioctadecyl-N.N-dimethyl-ammonium chloride was which had been removed and which had been treated calculated.

with a solution of 0.5 gm/liter of ditallowalkyldimethylarnmonium chloride. The average values obtained 5 11.;

from the handle determinations were given in the fol- [d 1 W lowing Table ll. According to the values of Table 11 even the first treatment of the prehardened sample of and for the avera Value fabric with the textile softeners used according to the 311 1:30 invention ave a full and soft handle. 1 1 1 g a= AJZIOUX X 2, -n a TABLE ll l Fl 1! Substance according Handle values to Example No. a 1n the following lable 111 the manage absorptn 1t) values 5 and the average percentual improvement of 0.3 gm/liter 0.5 gm/liter I 3 u 1 g the absorpttvlty A for some selected substances of the 3 5: invention, based on the absorpttvlty of water as 100. 3 2.5 2.5 was recorded. 4 1,4 "1.0 5 2.6 2.5 TABLE 111 Substance for comparison 1Dioetadecyldimethyl- 3 U 2.5 Residual ammonium de) Active substance Act'ne absorpthe lmprm ement oi without softener 6.0 according to substance capacity the absorpthe Example No. lgmfl I S (9}) capacity A l? l TABLE HLCOminuej N.Ndioctadeeyl-N.N-dimethyl-ammomum chloride was calculated.

Residual Aclnc sul sliiltce Acthe ahsorPthe lmprmemcnt of according to substance capacity the absorpthe I.A lzmmple [\ov {gm/ll S li I capacity A lit) 5 ii 100 ['T I] (U I 0.3 77.7 I I 0.5 61.1 2w In the Table IV the measured absorption time I. the M) 0 absorption values a and the percentual improvement B (um 3 y for some uaternary allo hanoylmeth 'lammonium n -4. IDWRRMHIIP compounds are given.

TABLE IV Residual Improvement of Concentration of Absorption ubsorpthity the ahsorpthe Actiue substance ucactive substance time capacit} capacity cording to Etample No. (g/ll tlseel a 1%] B (Q?! 1 ll. 57 87.7 250 (1.. hf: 75.8 2llll I 0.3 70 65.7 lbll (I 5 HI] 49.5 98 Untreated samples 50 100.0 Comparison (I 100 35 tDioctadec} ldimeth} l (I. 5 200 ammonium chloride! melhylammunium chloride) 0.5 15.7

c. Determination of the absorptive capacity (measurement of spreading time) The influrence of the textile softeners, used according to the imention. on the absorptivity of cotton test fabrics. softening rinsed with these preparations. was also determined by the method of Ox and Schuster [Schusten Textil-Rundschau 20. 352 1965)]. Here the spreading-out time t of water in a horizontally spread cotton test strip under exactly defined conditions with the use of an absorptivity value meter was determined. As test material, a cotton test fabric. previously extracted with methanol and dichloromethane. was used. It was agitated for minutes with a disper sion of the test preparation (cone. 0.3 and 0.5 gm/l); subsequently dried and airconditioned. A fabric analogously treated with water served as a comparison sample. The measurement was done with an absorptivity value meter. according to Ox and Schuster, the distance of the measuring contacts was adjusted to 5 cm and a dropping time of 10 see. was selected. In the normal case ten parallel measurements were carried out.

The absorption time is, according to the true dimension (sec/cm l, a reciprocical speed. An increase. therefore. corresponds a decrease in the absorptivity of the fabric.

lf 1,- is designated as the absorption time of the fabric rinsed with the preparation i and t the absorption time of the fabric rinsed with water. for the absorption value, that is the residual absorptivity of the soft-rinsed fabric. referred to the sample treated with water I 100%, the following equation is used.

As comparison also the absorption time t of a test fabric rinsed with a solution of 0.3 and 0.5 gm/l of N,N- dioctadecyl-NNdimethyl-ammonium chloride was determined and from it the percentual improvement B of the absorptivity of the preparations i with reference to According to both methods of determination of the absorption capacity. values were obtained according to which, compared with the known textile softener, which makes the fabric strongly hydrophobic, samples of fabric treated with the substances according to the present invention have a substantially better absorption capacity.

The following Examples 8 to 10 describe liquid washing after-treatment compositions. in which the substances of Formula I are used according to the present invention. In the production of the liquid composition the substance of Formula I was converted at 50 to 60C into a homogeneous melt with the dispersing agent and optionally an organic solvent as well as in some cases other additives. The acid and optionally the optical brightener, were dissolved in water and this aqueous solution was added with vigorous stirring to the abovementioned melt. The preparations so obtained are marked by a good pourability and dispers ibility in water. Perfumes and dyestuffs may be mixed with the preparations.

EXAMPLE 8 6.0% by weight of N,N-Didodecyl-N-methyl-Nal|0- phanoylmethylammonium chloride: 2.0% by weight of an adduct of oleyl-cetyl alcohol 5 mol ethylene oxide; 1.0% by weight of glycollic acid; Remainder water.

EXAMPLE 9 6.0% by weight of N.N-Ditetradecyl-N-allophanoylmethylammonium chloride;

5.0% by weight of isopropyl alcohol;

1.0% by weight of an adduct of coconut alcohol (C 2ClH) ethylene oxide;

0.5% by weight of tartaric acid;

02 1% by weight of cotton brightener of Formula III in which R, signifies the anilinoand R the morpholino residue;

1.0% by weight of N-benzyl-N-dodecyl-N,N-dimethylammonium chloride;

Remainder water.

EXAMPLE 10 6.0% by weight of N.N-Dicoconut-alkyl-Nanethyl-N- allophanoylmethylammonium chloride; 1.5% by weight of an adduct of cetyl-oleyl alcohol mol ethylene oxide; 0. l7r by weight of cotton brightener of Formula III in which R, signifies the anilinoand R the dihydroxyethylamino residue; 0.3% by weight of 2-hydroxy-2',4,4'-trichlorodiphen ylether; 0.5% by weight of citric acid; 5.0% by weight of isopropyl alcohol; Remainder water.

The following Example describes the preparation and composition of pulverulent washing after-treatment agents for laundry according to the invention.

EXAMPLE l l Pulverulent washing after-treatment composition 15.0% by weight of N.N-Di-tallow-alkyl-N-methyl-N- allophanoylmethylammonium chloride;

3.0% by weight of an adduct of nonylphenol +.9.5

mol ethylene oxide;

[5% by weight of glycollic acid;

55.0% by weight of urea;

20.5% by weight of sodium sulfate (anhydrous).

The preparation according to Example 11 was prepared as follows: the textile-softening compound and the nonionic dispersing agent were melted to a homogenous mixture at 50 to 60C. Simultaneously, the organic acid and the carriers were dissolved in water, preheated to 50C, and the above-named melt was stirred into this solution. The amounts were utilized so that l kg of all the ingredients of the washing after-treatment agent of the above composition was allotted to 5 liters of water. The dispersion thus obtained was atomized in a spray tower at [50C. A white, fine-grained and readily pourable powder resulted. To the finished preparation perfumes and anti-microbial active substances may be added.

The preparation of the composition of Example 11 could also be prepared as follows:

a. The textile softener, nonionic and glycolic acid (as a 70% solution) were mixed with water at 55C to give a slurry. The liquid mixture was sprayed at this temperature with the aid of a spraying apparatus into a rotating drum and onto the powdery carrier substances. The latter consisted of a mixture of calcined sodium sulfate of a bulk weight of 460 gm/l and of urea of a bulk weight of 485 gm/l. After the spraying, the product mixture was agitated for another minutes in the drum. Other specified products, according to the invention, can also be prepared by this method.

b. The textile softener and the nonionic dispersing agent were melted together at 50C to 60C to a homogenous mixture and simultaneously glycolic acid. sodium sulfate and urea were mixed at 50C with a 2 /2- fold amount of water. The abovenamed melt was stirred into this mixture and the slurry. thus obtained, was brought onto a roller-drier, whose rolls had a temperature of 140C. The product, after evaporation of water, was formed as a thin solid layer, that was lifted off the rolls in the form of scales. The scales were converted into a powder by grinding. Other specified preparations, according to the invention, can also be prepared by this method.

The washing after-treatment agents for laundry according to the invention are marked by a rapid dispersibility and distribution in cold water, so that the action of the textile softener, for example on use in the last rinsing cycle of a washing machine, is effective. The treatment with the preparations of the invention at a concentration of 0.3 gm of the textile softener per liter of rinsing bath already leads to a full and soft handle of the finished textiles. which are also marked by a good absorption capacity.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood. however, that other expedients known to those skilled in the art. or disclosed herein may be followed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. A liquid or powdery softening agent composition for washed textiles consisting essentially of a. from 1 to 50% by weight of a quaternary allophanoylmethylammrmium compound having the formula wherein R and R are individually members selected from the group consisting of alkyl having [0 to 24 carbon atoms, alkenyl having 10 to 24 carbon atoms and alkadienyl having 10 to 24 carbon atoms, R is a menr ber selected from the group consisting of alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms and cyanoalkyl having from 1 to 4 carbon atoms, R 4 and R are individually members selected from the group consisting of hydrogen and alkyl having I to 3 carbon atoms, and X represents the union of an acid selected from the group consisting of inorganic acids and organic acids having I to 4 carbon atoms,

b. from 0 to I09! by weight of at least one nonionic surface-active dispersing agent selected from the group consisting of a water-soluble dispersing agent and a watendispersible dispersing agent, and

c. the remainder up to l007r by weight of at least one diluent selected from the group consisting of water, and water-soluble or readily water-dispersible liquid carriers selected from the group consisting of alkanols having 1 to 5 carbon atoms, alkanones having 3 to 6 carbon atoms, and ethylene glycol and diethylene glycol and their monomethyl, dimethyl, monoethyl and diethyl ethers, and solid, inert, water-soluble or readily water-dispersible inorganic and organic compound carriers.

2. The liquid or powdery softening agent composition of claim 1 wherein R and R are alkyl having 12 to l8 carbon atoms.

3. The liquid or powdery softening agent composition of claim 1 having a further component of from 0.2 to 6% of an acid additive selected from the group consisting of inorganic acids innocuous to the fibers to be treated. organic acids having from 2 to 8 carbon atoms innocuous to the fibers to be treated and their slightly acidic water-soluble salts.

4. The composition of claim I wherein said diluent is selected from the group consisting of water, said liquid 19 carriers and mixtures thereof in an amount of from 74 to 97.8% by weight.

5. The composition of claim 1 wherein said diluent is a finely-divided solid selected from the group consisting of inert water-soluble. finely-divided solids and inen. readily water-dispersible. finely-divided solids. in an amount of from 40 to 98.8% by weight.

6. The powdery composition of claim wherein said solid is finely-divided solid diluent selected from the group consisting of urea. acetamide, biuret. sodium sulfate. solid polyethylene glycols and mixtures thereof.

7. A liquid softening agent composition for washed textiles consisting essentially of a. from 2 to by weight of a quaternary a1lophanoylmethylammonium compound having the formula wherein R and R are individually members selected from the group consisting of alkyl having 10 to 24 carbon atoms. alkenyl having 10 to 24 carbon atoms and alkadienyl having 10 to 24 carbon atoms. R is a member selected from the group consisting of alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms and cyanoalkyl having from 1 to 4 carbon atoms. R, and R are individually members selected from the group consisting of hydrogen and alkyl having l to 3 carbon atoms, and X" represents the anion of an acid selected from the group consisting of inorganic acids and organic acids having 1 to 4 carbon atoms,

b. from 0.2 to 6% by weight of at least one nonionic surface-active dispersing agent selected from the group consisting of a water-soluble dispersing agent and a water-dispersible dispersing agent.

c. from 0.3 to 7.5% by weight of at least one of the following conventional ingredients in the following amounts:

from 0.2 to 3% by weight of antimicrobial active compounds.

from 0.2 to 6% by weight of said acid additives selected from the group consisting of inorganic acids innocuous to the fibers to be treated, organic acids having from 2 to 8 carbon atoms innocuous to the fibers to be treated and their slightly acidic water-soluble salts.

from 0.01 to 0.5% by weight of cotton optical brighteners.

from 0.01 to 0.5% by weight of polyamide optical brighteners.

from 0.01 to 0.5% by weight of perfumes, and

from 0.00001% to 0.05% by weight of dyes,

d. from 1.0 to 15.0% by weight of water-soluble organic solvents selected from the group consisting of alkanols having 1 to 5 carbon atoms. alkanones having 3 to 6 carbon atoms. and ethyleneglycol and diethylene glycol and their monomethyl. dimethyl. monoethyl and diethyl ethers. and

e. the remainder up to 100% by weight of water.

8. A powdery softening agent composition for washed textiles consisting essentially of 20 a. from 5 to 25% by weight of a quaternary allophanoylmethylammonium compound having the formula wherein R and R are individually members selected from the group consisting of alkyl having 10 to 24 carbon atoms. alkenyl having 10 to 24 carbon atoms and alkadienyl having 10 to 24 carbon atoms, R is a member selected from the group consisting of alkyl having 1 to 4 carbon atoms. hydroxyalkyl having 1 to 4 carbon atoms and cyanoalkyl having from 1 to 4 carbon atoms. R and R are individually members selected from the group consisting of hydrogen and alkyl having 1 to 3 carbon atoms. and X represents the anion of an acid selected from the group consisting of inorganic acids and organic acids having 1 to 4 carbon atoms,

b. from 1 to 6% by weight of at least one nonionic surface-active dispersing agent selected from the group consisting of a water-soluble dispersing agent and a water-dispersible dispersing agent,

c. from 0.3 to 15% by weight of at least one of the following conventional ingredients in the following amounts from 0.2 to 3.0% by weight of an antimicrobial active substance,

from 0.2 to 6.0% by weight of acid additives selected from the group consisting of inorganic acids innocuous to the fibers to be treated. organic acids having from 2 to 8 carbon atoms innocuous to the fibers to be treated and their slightly acidic water-soluble salts.

from 0.01 to 0.5% by weight of a cotton brightener,

from 0.01 to 0.5% by weight of a polyamide brightener.

from 0.01 to 0.5% by weight of perfume, and

from 0.00001 to 0.05% by weight of dyestuff. and

d. the remainder up to by weight of solid, inert. water-soluble or water-dispersible inorganic and organic compound carriers.

9. A process for the softening of washed textiles which consists of rinsing said washed textiles with water containing from 0.05 to 1.0 gm/l of a quaternary allophanoylmethylammonium compound having the formula wherein R. and R are individually members selected from the group consisting of alkyl having 10 to 24 carbon atoms. alkenyl having 10 to 24 carbon atoms and alkadienyl having 10 to 24 carbon atoms, R is a member selected from the group consisting of alkyl having 1 to 4 carbon atoms. hydroxyalkyl having 1 to 4 carbon atoms and cyanoalkyl having from 1 to 4 carbon atoms, R and R are individually members selected from the group consisting of hydrogen and alkyl having 1 to 3 carbon atoms. and X represents the anion of an acid selected from the group consisting of inorganic acids and organic acids having 1 to 4 carbon atoms. drying said textiles and recovering said softened, washed tex- 

1. A LIQUID OR POWERDERY SOFTENING AGENT COMPOSITION FOR WASHED TEXTILES CONSISTING ESSENTIALLY OF A. FROM 1 TO 50% BY WEIGHT OF A QUARTERNARY ALLOPHANOYLMETHYLAMMONIUM COMPOUND HAVING THE FORMULA
 2. The liquid or powdery softening agent composition of claim 1 wherein R1 and R2 are alkyl having 12 to 18 carbon atoms.
 3. The liquid or powdery softening agent composition of claim 1 having a further component of from 0.2 to 6% of an acid additive selected from the group consisting of inorganic acids innocuous to the fibers to be treated, organic acids having from 2 to 8 carbon atoms innocuous to the fibers to be treated and their slightly acidic water-soluble salts.
 4. The composition of claim 1 wherein said diluent is selected from the group consisting of water, said liquid carriers and mixtures thereof in an amount of from 74 to 97.8% by weight.
 5. The composition of claim 1 wherein said diluent is a finely-divided solid selected from the group consisting of inert water-soluble, finely-divided solids and inert, readily water-dispersible, finely-divided solids, in an amount of from 40 to 98.8% by weight.
 6. The powdery composition of claim 5 wherein said solid is finely-divided solid dIluent selected from the group consisting of urea, acetamide, biuret, sodium sulfate, solid polyethylene glycols and mixtures thereof.
 7. A liquid softening agent composition for washed textiles consisting essentially of a. from 2 to 20% by weight of a quaternary allophanoylmethylammonium compound having the formula
 8. A powdery softening agent composition for washed textiles consisting essentially of a. from 5 to 25% by weight of a quaternary allophanoylmethylammonium compound having the formula
 9. A process for the softening of washed textiles which consists of rinsing said washed textiles with water containing from 0.05 to 1.0 gm/l of a quaternary allophanoylmethylammonium compound having the formula 